Amine and sulfur-containing alkylphenoxides

ABSTRACT

Novel dispersant detergents are provided by combining, at an elevated temperature, a sulfurized alkylphenol and a Mannich base - prepared from formaldehyde, alkylphenol, and a lower alkyl monoamine - in the presence of an alkaline earth metal base and a liquid hydroxylic compound, so as to prepare the alkaline earth metal salt of a chemically combined sulfurized alkylphenol and Mannich base. The compositions which are detergent dispersants also provide antioxidant activity and alkalinity reserve.

United States Patent [191 Abbott et al.

AMINE AND SULFUR-CONTAINING ALKYLPHENOXIDES Inventors: Andrew Doyle Abbott, Greenbrae;

Thomas V. Liston, San Rafael, both of Calif.

Chevron Research Company, San Francisco, Calif.

Filed: Oct. 27, 1972 Appl. No.: 301,697

Related US. Application Data Division of Ser. No. 186,494, Oct. 4, 1971, Pat. No. 3,741,896, which is a continuation-in-part of Ser. No. 97,300, Dec. 1 l, 1970, abandoned.

Assignee:

[ Oct. 14, 1975 [56] References Cited UNITED STATES PATENTS 3,458,495 7/1969 Younghouse et a]. 260/136 Primary Examiner-R. V. Hines Attorney, Agent, or FirmG. F. Magdeburger; C. J. Tonkin ABSTRACT Novel dispersant detergents are provided by combining, at an elevated temperature, a sulfurized alkylphenol and a Mannich base prepared from formaldehyde, alkylphenol, and a lower alkyl monoamine in the presence of an alkaline earth metal base and a liquid hydroxylic compound, so as to prepare the alkaline earth metal salt of a chemically combined sulfurized alkylphenol and Mannich base. The compositions which are detergent dispersants also provide antioxidant activity and alkalinity reserve.

8 Claims, No Drawings AMINE AND SULFUR-CONTAINING ALKYLPHENOXIDES CROSS-REFERENCES TO RELATED APPLICATION This is a division, of application Ser. No. 186,494,

filed Oct. 4, 1971 now US. which is a continuation-inpart of application Ser. No. 97,300, filed Dec. 1 1, 1970 now abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention Lubricating oils used under the severe conditions of diesel engines are highly compounded so as to provide neutralization of acids derived from the sulfur in the fuel and oxidation of hydrocarbons, both of the fuel and oil; dispersancy so as to maintain sludge-forming precursors dispersed in the oil; improved wear protection and oiliness properties; as well as enhancing other attributes of the oil. In addition to the requirements normally attendant to a diesel lubricating oil, those oils which find use in railway diesel engines have the additional factor of not being corrosive or reactive to silver. Silver bearings are used in a preponderant number of diesel engines today.

The desirability of having a single additive providing multifunctional properties is evident in the efficiency and economies in the manufacturing and using of a single additive as compared to a plurality of additives. However, because of the severe operating conditions under which alubricating oil performs in diesel engines, it is frequently found that additivesfwhile effectively performing a particular function, will tend to degrade and enhance deposit formation. Therefore, in designing any particular additive, it is essential not only that it fulfill the function(s) for which it has been designed, but that it be stable under the conditions of use or degrade slowly to materials which do not enhance deposit formation.

2. Description of the Prior Art Alkaline earth metal phenoxides or phenates have been used in lubricating oils for a long period of time. Both sulfurized alkylphenols and Mannich bases have been employed in lubricating oils. U.S. Pat. Nos. 2,459,1 l4 and 2,459,116 teach the preparation of Mannich products employing polyamines with sulfurbridged alkylphenols. US. Pat. No. 3,454,497 prepares a Mannich base using methyl amine, formaldehyde and alkylphenols for use in lubricating oils. Other patents of interest include US. Pat. Nos. 2,810,697, 3,372,118, 3,429,812, 3,472,773, 2,527,279, 2,763,616, 3,368,972, 2,410,911, 2,962,442, 3,413,347, and 3,340,190.

SUMMARY OF THE INVENTION New detergent dispersant phenates having alkalinity reserve and antioxidant activity are prepared by the simultaneous neutralization of a sulfurized alkylphenol and a Mannich base prepared from a lower alkyl amine, an alkylphenol and formaldehyde. The neutralization is carried out at elevated temperatures with an alkaline earth metal base in the presence of a hydroxylic solvent under conditions to minimize the loss of amine nitrogen.

DESCRIPTION OF THE SPECIFIC EMBODIMENTS The compositions of this invention are the reaction products of an alkaline earth metal base, oxide or bydroxide, a Mannich base prepared from formaldehyde, alkylphenol, and a primary lower alkyl amine and a sulfurized alkylphenol. The reaction is carried out at elevated temperatures so that molecular bonds are formed between the Mannich base and the sulfurized alkylphenol in addition to those bridging bonds created by the divalent alkaline earth metal.

The product as formed (independent of any diluent) will have an alkalinity value (ASTM Test-D2896) in mg. KOH/g. in the range of to 450, more usually about to 400.The product will provide in elemental analysis from about 4 to 12, more usually from about 5 to 10, weight percent calcium, at least about 0.1 to 5, more usually from about 0.5 to 4, weight percent nitrogen, and from about 0.8 to 10, more usually from about 2 to 8, weight percent sulfur. In a 100 neutral oil, (100 being the viscosity at 100F in SUS) at an alkaline earth metal concentration of 0.88 formal (3.5 weight percent for Ca), the viscosity at 210F. will normally be in the range of about 200 to 3,000 SUS, more usually in the range of 500 to 1,500 SUS.

The compositions of the subject invention are com plex in nature. It is believed that a substantial proportion of the composition corresponds to one of the following formulae:

wherein: A is CH --CH.

N l R B is S) atoms, the average number of carbon atoms generally being in the range of about 10 to 20 R is lower alkyl, usually of from 1 to 3 carbon atoms, and preferably of 1 carbon atom, namely, methyl. The ratio over the entire composition of the equivalents of alkylphenol from the Mannich base to equivalents of alkylphenol from the sulfurized alkylphenol will normally be 0.2-:1, more usually 0.3-3zl, and preferably 0.32:1.

The remaining valences of the oxygen atoms are satisfied by an alkaline earth metal. These metals are calcium and barium, preferably calcium. Both valences of the metal may be satisfied by the phenoxide or one valence by the phenoxide and the other valence by an alkoxide or hydroxide, the group varying with the hydroxylic solvent employed and the proportion of alkaline earth metal used in the reaction. A few of the phenoxide groups, not exceeding mole percent, may be bonded to hydrogen, depending on the amount of excess of alkaline earth metal present.

The compositions of this invention are prepared by combining in a suitable reactor the Mannich base and sulfurized alkylphenol in an equivalent ratio (based on phenol) in therange of 0.25:l, more usually 0.33:l. In addition to the above reactants are included an alkaline earth metal oxide or hydroxide, preferably hydroxide, and a hydroxylic solvent, usually ethylene glycol.

The amount of alkaline earth metal base will depend on the method of preparation of the sulfurized alkylphenol. To the degree that an alkaline earth metal base was employed during the preparation of the sulfurized alkylphenol, the added amount of alkaline earth metal base will provide a total of at least one equivalent of alkaline earth metal present per equivalent of alkylphenol present, usually not exceeding 1.75 equivalents, and more usually not exceeding 1.5 equivalents of alkaline earth metal per equivalent of phenol present.

The amount of the hydroxylic solvent will vary with the particular solvent employed. Ethylene glycol, propylene glycol, and methanol are examples of suitable solvents. Since ethylene glycol is the preferred solvent, only its use will be discussed in detail. The amount of ethylene glycol employed will normally be from about 5 to 35 weight percent, preferably from about 7 to 20 weight percent, of the total reaction mixture.

In addition to the ethylene glycol, inert hydrocarbon diluent may also be present. These inert diluents may serve to aid in the handling of the reactants, lowering the viscosity of the reaction mixture, and enhancing the ease of isolation of the product. In view of the use of the subject compositions, mineral oils of lubricating viscosity may be employed and the product isolated as a solution in the mineral oil. Normally, the inert diluent will be present in the reaction mixture, if at all, in amounts of from 3 to 65 weight percent, more usually 5 to 50 weight percent of the total reaction mixture.

Conveniently, a small amount of an anatifoaming agent or foaming suppressant may be employed. The foam suppressant will normally be present in the reaction mixture in amounts of 1 X 10* to 1 X 10 weight percent. Foam suppressants are conventional and need not be exemplified here. i

The reaction is conveniently carried out by combining the sulfurized alkylphenol, the Mannich base, the

alkaline earth metal oxide or hydroxide, and ethylene glycol. As already indicated, an inert diluent may also be present. Preferably, prior to the addition of the ethylene glycol, the mixture is heated to at least C., but below the temperature at which the reaction is to be carried out, normally below 140C.

After addition of the ethylene glycol, the temperature is raised so as to distill water overhead, removing the water of reaction. The temperature is then raised, not to exceed 200C. The pressure is reduced to permit the distillation of ethylene glycol. Usually, the temperature during removal of water will range from to 160C., while the temperature during removal of ethylene glycol will range from to 200C., preferably from to 180C. The pressure will vary, depending on the temperature and rate of distillation desired. The reduced pressure may vary from about 0.01 to 0.8 atmosphere.

The time required for the removal of water will usually be from about 30 minutes to 3 hours. The time for the removal of ethylene glycol will normally be about 30 minutes to 9,hours. The time for the reaction, that is, from the initial removal of water to substantially complete removal of ethylene glycol, will vary from about 1 hour to 6 hours. The time, while not a critical factor, should not be unduly protracted, and will depend on the capacity of the equipment, the amount of reactants, the degree of foaming and the ability to control the temperature and rate of removal of distillates.

When no further ethylene glycol comes over, the reaction mixture may be cooled. Depending on the presence and amount of inert diluent, the temperature should preferably be maintained above about 150C. prior to sufficient dilution with a convenient solvent. The mixture can become extremely viscous, and solution into a solvent is difficult below a temperature of about 150C. Any convenient solvent may be used, but

in view of the intended use, normally a hydrocarbonaceous lubricating oil will be used as the diluent. Depending on the end use, various hydrocarbonaceous lubricating oils may be employed. As diluted, the product is ready to be employed, after filtration, as a concentrate for formulating finished lubricating oils.

The various reactants will now be considered. The first and simplest reactant is the alkaline earth metal oxide or hydroxide. As already indicated, these are calcium and barium, preferably calcium. With calcium, normally calcium hydroxide will be employed.

Sulfurized alkylphenols are well known materials for use in lubricating oils. The method of preparation of the sulfurized alkylphenols is not critical to this invention. The sulfurized alkylphenol should have at least about 4 weight percent sulfur and not more than about 20 weight percent sulfur, more usually from about 8 to 18 weight percent sulfur. Preferably, there will be at least 0.5, and not more than about 12 weight percent sulfur, based on the weight of the sulfurized phenol composition present which is not involved in bridging or is involved in bridges having at least 3 sulfur atoms. Usually, there will be present about 1 to 9 weight percent sulfur, based on the weight of sulfurized phenol composition which is in a form for a bridging reaction.

The sulfurized alkylphenols will, for the most part, have the following formula:

OH OH wherein R is alkyl of from 8 to 36 carbon atoms, more usually of from to 24 carbon atoms with the average number of carbon atoms being in the range of about 10 to 20, y is an integer of from 1 to 9, more usually of from 1 5, averaging over the entire composition in the range of about 2 to 4, and n is an integer of from 1 to 5, more usually of from 1 to 3. There may be small amounts, not more than about 10 weight percent, of sulfurized phenol having y greater than 9. i

The aliphatic hydrocarbon groups designated R may be in the ortho, meta, or para positions, but will predominate in the meta or para positions. Since branched-chain alkyl groups tend to minimize the amounts of ortho-substituted phenols, the branchedchain alkyl groups are preferred. However, it should be realized that to some extent the alkyl groups are in the ortho position, and ortho substituted phenols act as chain terminators in the copolymerization of sulfur and alkylphenol.

The sulfurized alkylphenol can be prepared by combining alkylphenol, sulfur, calcium oxide, or calcium hydroxide and glycol at an elevated temperature, driving off the water and hydrogen sulfide, followed by isolation of the sulfurized alkylphenol. See, for example, US. PatjNo. 2,989,466. Sulfur monochloride may also be used to prepare sulfurized alkylphenols, frequently employing a Friedel-Crafts catalyst to aid the reaction. Various methods of preparing sulfurized alkylphenols may be found in US. Pat. Nos. 2,362,289, 2,451,345, 2,744,083, and 3,367,867.

The Mannich bases which are employed are prepared by combining at'elevated temperatures, an alkylphenol, formaldehyde, and a primary lower alkylamine, preferably of from 1 to 3 carbon atoms, and particularly preferred, methyl amine. A method for preparing the Mannich bases may be found in copending application Ser. No. 22,452, filed on Mar. 25, 1970. US. Pat. No. 3,454,497 describes an additional method for preparing Mannich bases employing primary amines.

The Mannich bases will, for the most part, have the following formula:

R OH

wherein R is lower alkyl, usually of from 1 to 3 carbon atoms, and preferably of 1 carbon atom, methyl, R is saturated aliphatic hydrocarbon of from 8 to 36 carbon atoms, more usually of from 10 to 24 carbon atoms, and normally having an average number of carbon atoms in the range of from 10 to 20, x will range from 1 to 19, usually averaging in the range of 4 to 9. There may be small amounts, less than 10 weight percent, of

Mananich bases having x greater than 19. The average over the entire composition will normally be in the range of 3 to 9, with more than 50 weight percent of the composition having x equal to 3, or higher.

The Mannich base will normally be prepared from alkylphenols having less than 25 mole percent, preferably less than 20 mole percent ortho substitution. The Mannich base in the invention will have less than 20, usually less than 10, number percent of attachment of the Mannich amine at the position para to the hydroxyl group of the phenol.

The Mannich base (undiluted) will have at least 2 weight percent nitrogen and normally not more than about 5 weight percent nitrogen, the amount of nitrogen normally being in the range of about 2.2 to 4.0. The average molecular weight, as determined by osmometry, will be at least 600, more usually at least 700, and normally not exceeding about 5,000.

The following examples are offered by way of illustration and not by way of limitation. (All parts are by weight, unless otherwise indicated.)

EXAMPLE 1 Into a reaction vessel are introduced 8,825 parts of sulfurized alkylphenol (prepared as described in Example A), 10,350 parts of a Mannich base (prepared as described in Example B) as a 60 weight percent solu tion in a mid-continent neutral oil, 2 parts of DC- 200 foam inhibitor, and 1,640 parts of calcium hydroxide. The mixture is heated at 250275F. and 5,150 parts of ethylene glycol added. The pressure is then reduced to 20 inches mercury and the mixture heated to 300F. over a period of 50-70 minutes while water is removed overhead. When substantially all of the water is removed, the temperature is then raised to 375F. over a period of 2 to 3 hours. The pressure is concomitantly reduced so that the maximum vacuum is reached at about the time the temperature reaches 340F. The final pressure on the kettle is not greater than 50 milli meters of mercury. When the temperature of 370F. is achieved, this temperature and the maximum vacuum is held for 30 minutes.

The mixture is then cooled rapidly to 300F. and nitrogen introduced into the system to atmospheric pres sure. To the mixture is then charged 4,500 parts of 100 neutral oil and the solution mixed for 30 minutes while maintaining the temperature at about 250F. The product may then be isolated.

The above product will have about 4.2 weight percent calcium and a viscosity of about 4,000 SUS at 210F.

EXAMPLE A Into a reaction vessel are introduced 18,100 parts of polypropylphenol (prepared from polypropylene of from about 12 to 15 carbon atoms), 750 parts of calcium oxide and 4,620 parts of sulfur, the temperature of the mixture being maintained at 220F. The temperature is then raised to 265275F. and 580 parts of ethylene glycol charged. Hydrogen sulfide begins to be evolved and a low rate nitrogen purge is then begun over the top of the reactor. The temperature is slowly raised to 335-340F. and the temperature maintained for a period of 6 hours. At the end of this time, the mixture is cooled to about 225250F. and the product may be isolated.

EXAMPLE B Into a reaction vessel is introduced 60.4 parts of polypropylphenol (prepared from polypropylene of from about 12 to carbon atoms) and the system degassed and purged with nitrogen. After the purging iscompleted, 17.9 parts of isobutyl alcohol and 14.5 parts of paraformaldehyde are added vwhile the mixture is agitated. To the mixture is then added 7.2 parts of liquid methyl amine, the addition requiring 3 hours. The temperature, during the addition, is maintained at 120150F.

After completion of the addition of the methyl amine, the mixture is stirred for an additional 15 minutes and the vessel vented. The temperature is then raised to 190F., the vessel closed, and the temperature raised to 260F. The temperature is maintained for a periodof 7 hours, while a pressure of psig is maintained. The product may then be isolated by washing with water and then distilling the isobutyl alcohol.

If desired, the product may be diluted with an inert diluent for convenient handling. The product is then heated in vacuo for about minutes at 300., following which it is ready for use in the final reaction.

EXAMPLE 2 Into a reaction vessel were introduced 8,643 grams of sulfurized alkylphenol (unfiltered), 9,255 grams of the Mannich base, as a-66 weight percent solution in 100 neutral oil, and 1,618 grams of calcium hydroxide, followed by the addition of 5,122 grams of ethylene glycol and 4 grams of DC-200, a foam suppressant.

(The sulfurized alkylphenol was prepared as described in Example A, filtered, and had the following specifications (neat): The alkylphenol was polypropylene phenol having alkyl groups of from 12 to 15 carbon atoms; alkalinity value mg. KOH/g., 63.6; Ca, 2.27; S, 14.99; viscosity of 210F., SUS, 2740.)

The Mannich base was prepared from polypropylene alkylphenol (polypropylene of from 12 to 15 carbon atoms) as described in Example B. The product had the following specification, as a 66.7 weight percent solution in a mid-continent 100 neutral oil: N, 2.74; alkalinity value, mg. KOH/g, 109; viscosity at 210F., SUS, 425.)

The mixture was heated rapidly to 265F. and a 10 inch Hg vacuum applied, water and hydrogen sulfide being removed overhead. The pressure was decreased and the temperature raised over a period of 4 hours and .After some difficulty, the product was dilutedfurther with mid-continent neutral oil and filtered using a .mixture of Celite 573 and Celite 545. The filtered product weighed 15,457 grams. N, 0.60, Ca, 3.35,%S,-3.12.

EXAMPLE 3 Into a reaction vessel were introduced 427 grams (1.2.8 equivalents) of sulfurized alkylphenol and 454 grams (0.93 equivalent) of theMannich base described in Example 2 as a 66.7 weight percent active solution,

the mixture heated to 95C., and 253 grams of ethylene glycol and 80 grams (2.16 equivalents). of calcium h ydroxide added, The pressure was reduced to 10 inch vacuumand water collected overhead as the temperature was raised to C. The temperature was then raised to 150C. over a 55 minute period, followed by slowly reducing the pressure to 25 mm. Hg, while slowly raising the temperature to 182C. The temperature was maintained for 15 minutes, and then the reaction mixture was allowed to cool, nitrogen being introduced tobreak the vacuum. The product was then diluted with 300 grams of a mid-continent 100 neutral oil. The oil solution was then filtered through Celite, the filtered product weighing 1,105 grams. Analysis: Ca, 4.43, 4.24; N, 0.82, 0.82; S, 3.56; alkalinity value, mg. KOH/g., 152.5, 151.4.

The sulfurized alkylphenol employed above was prepared as described in Example A and had the following specifications: S, 14.9; alkalinity value mg. KOH/g., 62.7; Ca, 2.16, viscosity at 210F., sus, 2.435.

A number of additional examples were carried out following substantially identically the procedure of Example 3, except for variation in the ratio of sulfurized alkylphenol and Mannich base. Both thesulfurized alkylphenol and Mannich base were obtained from the' same batch preparation. The following table indicates the amounts of material employed, and the specifica tions in the final product. All of the specifications indi cated are based on .a composition which is 63 weight percent active in a mid-continent 100 neutral oil.

TABLE 1 Sulfurized Mannich Ethylene Calcium Mid-continent I Alkalinity Alkylphenol, Base, Glycol. Hydroxide, I00 Value. Example g g. g. g. Neutral Oil 7; N 7( Ca" "/1 S mg. KOH/g 1 66.7 weight percent active in mid-continent 100 neutral oil. Adtlcll at completion of reaction. Analysis carried out on diluted product.

20 minutes, the final temperature being 380F., and the 5 6 EXAMPLE 9 final vacuum about 48 mm. Hg. During this time, water and ethylene glycol were taken overhead. The mixture was cooled to 275F., the vacuum broken with the inlnto a reaction vessel were introduced 427 grams: of sulfurized alkylphenol. prepared as follows. i

Into a reaction vessel were added 3011 grams of polypropylene phenol (polypropylene of from 12 to 15 carbon atoms), the mixture heated to 150F. and 125 grams of calcium oxide added. The temperature was while maintaining a nitrogen atmosphere. To the reaction mixture was then added 18 g. of calcium hydroxide, 29 g. of ethylene glycol and one drop of DC 200. The temperature was then raised to 150C. and the raised to When 8 grams of Sulfur were pressure dropped to 200 mm. Hg. and these conditions Charged, followed y the addition 0f96 grams of y maintained for 30 minutes. The pressure was then reene glycol. The mixture refluxed for about minutes, d d to 50 mm H h temperature i d to 180C wrthhydregeh Sulfide Coming The temperature was and maintained for minutes. At the end of this time, eehtlhueusly increased until 34001? was reached, the the mixture was cooled to 100C. and filtered through temperature was then maintained for 6 hours at which 10 a 50 50 mixture f Cehte 512 and Dicahte 573 The h time the reaction mixture was allowed to cool and nin i was l A l i N, c 3 52- trogen introduced to provide an inert atmosphere. The AV mg OH/ 147 p e Werghed 3666 grams" ah alicluot was taken for The compositions of this invention find particular use analysts and hltered- Analysts: S, Alkalinity in lubricating oils where not only detergency and dis- Valtle, /gi 61-39 Whleh 15 equal to 15 persancy are desirable, but also acid neutralization ca- To the 427 grams of sulfurized alkylphenol was pacity and antioxidant activity added 454 grarhs of the Mannich base described in The compositions of this invention can be used with ample the rmftthre heated to 2000K, atwhleh time various base oils which find use as lubricating oils. Oils 80 grams of ealehlm hydrexrde and 253 grams of y of lubricating viscosity have viscosities in the range of glyeet were eharged- The temperature was 20 about to 50,000 SUS (Saybolt Universal Seconds) ralsed over a period of about 1 hour and 15 minutes to at 100 Normally, the i i h fi d use i hi i 3600B while the Pressure wasislowly reduced to a final vention will have viscosities at 210F. in the range of Pressure 9 After holding the temperature about 20 to 150 SUS, more usually from about to and Pressure for about 10 e i the rrhxture was 120 SUS. The hydrocarbon lubricating oils may be det allowed t0 e001 to 2500p ahltregeh atmosphere 25 rived from natural sources and be paraffinie, naph-. lhtreeueed and 300 grams of a mld'eehttherrt 100 thenie, or asphaltic based or mixtures thereof. Alternatral o1l added. The final product weighed 1 185 grams. tively, synthetic hydrocarbon oils may be used h y N, 0-71, S, Ca, atka' The compositions of this invention may also find use hhlty Value, o 134-9, in nonhydrocarbon synthetic oils such as esters, sili- A number of sulfurized alkylphenols were prepared 30 cates, etc. The various oils may be used together whenby the process described in Example A, where the sulever miscible or made so by mutual solvents. fur to alkylphenol ratio was varied. These compositions The compositions of this invention when formulated were then combined with Mannich base as prepared in as concentrates, will normally be from about 15 to Example B, substantially following the procedure of weight percent, more usually from about 30 to 60 Example 1. The following table indicates the sulfur to 35 weight percent. alkylphenol ratios, the analysis of the product, the anal- When used in formulations, depending on the particysis of the Mannich base and the analysis of the final ular formulation, the amount of the subject composiproduet. tion will generally vary from about 5 to 400 mM./kg.

TABLE ll Sulfurized Alkylphenol Combination of Sulfurized Alkylphenol and Mannich Base Product Sulfurized Mannich Analysis" Reaetant A.V.2 Alkylphenol Base A.V. Example Sulfur, parts '7r.S mg KOH/g. parts parts 7(.N 7:.Ca 7(.S mg KOH/g.

Combined with the sulfur were 125 parts of C00. 2900 parts of alkylphcnol (alkyl is polypropylene of from 12 to 15 carbon atoms). and 96 parts of ethylene glycol.

A.V. alkalinity value (ASTM D4896). "Prepared as described in Example B. 66.7 wt. '71 active in 100 neutral oil; lrN. 2.

In addition to the sulfurized ulkylphenol and Mannich base were used 253 parts of ethylene glycol. parts ofcalcium hydroxide and 300 parts ota mid-contincnt neutral oil. Analysis carried out on diluted product.

EXAMPLE 18.

lnto a reaction flask fitted with nitrogen bubbler was introduced 100 grams of 2,2'-bis( l hydroxy-4- polypropylenphenyl)disulfide (polypropylene of from 12 to 15 carbon atoms) as a 75 wt. solution in oil and grams of the Mannich base prepared as described in Example B as a 66.7 wt. active solution in a mid continent I00 neutral oil (alkalinity value mg. KOH/g, 108; N, 2.74) and the mixture heated to 100C.

based on metal, more usually from about 8 to 75 mM./kg. based on metal. Usually, in a railroad oil formulated composition, the alkalinity value is at least 5, more usually of at least 6 mg. KOH/g. and not more than about 15 mg. KOH/g.

Various other additives may also be present in the formulation. Of particular interest for use in combination with the subject additives are sulfurized aliphatic hydrocarbons. These compositions are well known in the art and tend to have from about 16 to 50 carbon atoms and vary from about 15 to 25 weight percent sulfur. These additives will be present in from 0.05 to 0.75 weight percent.

In addition to the sulfurized hydrocarbons, it is also advantageous to employ nonash-containing detergents and dispersants, to provide a low ash composition. These ashless detergent dispersants are primarily aliphatic polyols of from 2 to 6 hydroxyl group or alkylene polyamines (alkylene of from 2 to 3 carbon atoms) having from 3 to 5 amine nitrogen atoms, either directly bonded to an aliphatic hydrocarbon group of from about 30 to 200 carbon atoms, more usually from 50 to 125 carbon atoms, or indirectly to an acyl group, such as succinyl, phosphoryl, carboxyl, etc., where the acyl group has a hydrocarbon substituent and forms ester or polyester with the alcohols, and an amide or imide, e.g., succinimide, link to the alkylene polyamine. See US. Pat. Nos. 3,522,179, 3,331,776, 3,219,666 and 3,202,768, which disclose polyisobutenyl succinimides of alkylene polyamines (polyisobutenyl 'of from 50 to 200 carbon atoms; alkylene polyaminesalkylene of from 2 to 3 carbon atoms and polyamine of from 2 to 5 nitrogen atoms; succinic groups to alkylene polyamines being 1 2:1). The ashvless detergents will generally be present in from about 2.5 to weight percent, more usually from about 3 to 8 weight percent.

Other additives may also be present in minor amounts, such as additional ash-containing detergents, e.g. sulfonates, both neutral and overbased, phosphonates, both neutral and overbased, corrosion inhibitors, oiliness agents, pour point depressants, viscosity index improvers, etc.

In order to demonstrate the effectiveness of the subject compositions, a number of bench tests and engine tests were carried out, the results being provided in Table III infra.

The first test to be discussed is referred to as the Oxidation Test to determine antioxidant activity. To grams of the test oil is added 0.26 cc. ofa solution having 2268 ppm of copper, 6236 ppm of iron, 567 ppm of manganese, 4535 ppm of lead, and 4535 ppm of chromium, all as their naphthenates, providing a distri-- bution of metals which would be expected to be found in a used crankcase oil from a General Motors D-7l diesel engine. The oil sample to be tested is maintained The subject compositions were formulated in a 70 V.I. SAE 40 oil to simulate a commercial formulation. In the oil were employed 59 mM./kg. based on calcium of the test composition, 6 weight percent of a bis(- polyisobutenyl succinimide) of tetraethylene pentamine (mixed polyisobutenyl of about 640 and 1000 number average molecular weight), 22 mM./kg. based on calcium of calcium mahogany sulfonate (1.67 wt. Ca), 0.3 wt. of sulfurized paraffin having 17.5 wt. sulfur, and 0.025 wt. of terephthalic acid.

The second test to be discussed is the silver thrust washer test. In this test, a silver test piece is used made of fine silver, 99.9 percent pure, soldered to a backing of soft steel. Both silver and backing are nominally Vs inch in thickness, 1.3 inches OD and 1.0 inch ID. The silver surface is grooved by 3 equally spaced slots obtained by l; inch end mill chamfered 30 on its lower end. A. 0.0l-inch deep and H32 inch-wide slot is cut across the center of each of the three raised silver surfaces.

The silver test piece is annealed after machining and after each use to remove any work hardening in the silver. The annealing is carried out at 650F. for V2 hour, allowing to slowly cool to room temperature. Following annealing, both sides are surface lapped to obtain a smooth flat surface of approximately 9-12 microinches finish.

The steel test specimen is made to duplicate the metallurgy of the wrist pin steel in the EMD locomotive engine. The material is AISI Steel No. 8620H. Heat treatment to a minimum hardness of 58 Rockwell C is achieved by carburizing for 0.04-0.05 finish case depth, pit cool; reheating to 1,475F. and oil quenching; followed by tempering at 400F. for 8 hours. Both sides are finished-lapped to a finish of 35 microinches. Nominal dimensions are 1% inches OD, 0.9 inch ID, and 0.2 inch thick.

A motor-driven mechanism is used to obtain oscillatory motion at the test surfaces. A 20 cc. sample of fresh oil is employed in the oil cup, the apparatus assembled and the oscillatory motion begun. The apparatus is run for 10 minutes without heating. At the end of the 10 minutes, there is a 35-minute heatup as the temperature is raised to 350F., followed by 15 minutes of constant temperature operation at 350F. The load' during the test is maintained continuously at 4280 psi at the bearing surfaces by means of a calibrated spring. The wattage is recorded during the constant temperature operation as an indication of the work load. Also, the weight loss of silver is reported. (A sign indicates an increase in weight.)

Another test that was carried out was to determine the amount of sediment resulting upon the addition of sulfuric acid. Since diesel fuels contain sulfur and produce sulfuric acid, it is desirable to produce a minimum amount of sediment upon neutralization with sulfuric acid. The alkalinity value is determined of the sample to be tested, and the amount of cone. H 50 required to neutralize the sample is calculated. To a 50 gram sample is added 150 ml. n-heptane and the mixture stirred in a Waring blender. Sulfuric acid is added dropwise over a 5 minute period in an amount sufficient to neutralize the base present and the mixture then homogenized for 10 minutes. At the end of this time, the solution is divided between two ml. calibrated centrifuge tubes and then centrifuged at 2200 rpm for 0.5 hour. The sediment is read and the average of the two readings taken. The results are reported as ml. of sediment per 10 mg. KOH/g. of sample and ml. of sediment per I0 mg. KOH/g. of sample due to amine nitrogen.

For the Oxidator B test and the silver thrust washer test, the formulated oil described previously was employed. For the sediment test the sample prepared as a 63 percent active solution in I00 neutral oil was employed. .The following table indicates the results.

TABLE 111 Oxidation Test Silver Thrust Washer Sulfuric Acid Sediment. ml. 7: Vis. Increase Wt. loss. Watts per 10 A.V. Example in 10 Hrs. mg. 45 min. 60 min. per 10 A.V. Based on N In order to demonstrate the subject compositions acwherein:

tivity under severe conditions in a diesel engine, a 180 BMEP test was carried out. The one-cylinder diesel engine employed has a bore of 5 /8 inches and a stroke of 6 /2 inches. The brake horsepower is 55, and the engine is run at 7460 BTUs per minute and 1880 rpm, with R is an alkyl having from 1 to 3 carbon atoms, R is an alkyl having from 8 to 36 carbon atoms, at is an integer of from 1 to 19;

2. A sulfurized alkyl phenol of the formula:

I OH on the air temperature at 255F., the outlet water temperl ature at 190F., the oil to bearing temperature at As)", 205F., and a fuel which contains 1.0 weight percent sulfur. Using the formulation described previously, the test was run for 120 hours and the following results ob- 2 1 R2 tamed. R y

' TABLE IV Example Grooves Lands Underhead *Carricd out for only 118 hours. Oil contained (1.5 wt. 7: ofu sulfurized paraffin having 13% sulfur.

+Rcsults obtained at 60 hours. 0400. 100 being completely filled Ill-800, 800 being completely black 040, 10 being completely clean The above results demonstrate the excellent effec tiveness of the subject compositions under a wide variety of conditions. The subject compositions provide low sediment when neutralized in sulfuric acid. In addition, they significantly reduce the wear loss with silver bearings. Also of importance, under extremely severe conditions at high temperatures in a diesel engine, they are able to maintain a low level of deposits. in addition, they provide excellent antioxidant activity, minimizing viscosity increases in lubricating oils and are able to neutralize gross amounts of acids.

We claim:

1. A reaction product of l. a Mannich base of the formula:

wherein:

R is an alkyl having from 8 to 36 carbon atoms,

n is an integer of from 1 to 5; and

y is an integer of from 1 to 9; and

3. An alkaline earth metal base wherein the alkaline earth metal is selected from the group consisting of calcium and barium;

wherein the reaction of said Mannich base with said sulfurized alkylphenol and said alkaline earth metal base is conducted at a temperature between about C to about 200C and in the presence of ethylene glycol which is removed from the reaction system upon completion of the reaction, and wherein the ratio over the entire reaction product of the equivalents of alkylphenol from the said Mannich base to equiva lents of alkylphenol from the said sulfurized alkylphenol is from 0.2-5:1, the said alkaline earth metal base is used in an amount to provide a total of from 1 to about 1.75 equivalents of said alkaline earth metal base per equivalent of alkylphenol, and a solution of said reaction product at a concentration of 0.88 formal of calcium or barium in a 100 neutral oil has a viscosity of 210F in the range of about 200 to 3,000 SUS.

2. The reaction product according to claim 1, wherein said alkaline earth metal is calcium, said reaction product has an alkalinity value in the range of 130 to 450, from 4 to 12 weight percent calcium, and from 0.1 to 5 weight percent nitrogen.

3. The reaction product according to claim 1, wherein R is methyl.

4. The reaction product according to claim 1, wherein R is methyl, said ratio is 0.3-3:1, and said alkaline earth metal is calcium.

5. The reaction product according to claim 1, wherein said alkaline earth metal base is calcium hydroxide, R is methyl, and said reaction product has an alkalinity value of 175 to 400 mg. KOH/g., has from 0.5 to 4 weight percent nitrogen, 2 to 8 weight percent sulfur, and the solution of said reaction product in a 100 neutral oil at acalcium concentration of 0.88 formal has a viscosity in the range of 500 to 1,500 SUS at -7. The reaction product according to claim 6,

wherein R and R are polypropyl of from about 12 to 15 carbon atoms, and said alkaline earth metal base is Ca(OH) 8. A reaction product of 1. A Mannich base of the formula:

wherein:

R is lower alkyl, of from 1 to 3 carbon atoms, R is'polypropyl of from about 12 to 15 carbon atoms; x is an integer of from 4 to 9; 2. A sulfurized alkylphenol of the formula:

wherein: t

R is polypropyl of from about 12 to 15 carbon atoms;

n is an integer of from 1 to 5; and

y is an integer of from 1 to 5; and

3. A calcium base;

wherein the reaction of said Mannich base with said sulfurized alkylphenol and said calcium base is conducted'at a temperature of to C and in the presence of ethylene glycol which is removed from the reaction system upon the completion of the reaction, and wherein the ratio over the entire reaction product of the equivalents of alkylphenol from the said Mannich base to equivalents of alkylphenol from the said sulfurized alkylphenol is from 0.33;1, the said calcium base is used in an amount toprovide a total of from 1 to about 1.75 equivalents of said calcium base per equivalent of alkylphenol, and the solution of said reaction product at a concentration of 0.88 formal of calcium or barium in a 100 neutral oil has a viscosity at 210F in the range of about 500 to 1,500 SUS. 

1. A REACTION PRODUCT OF
 1. A MANNICH BASE OF THE FORMULA:
 2. The reaction product according to claim 1, wherein said alkaline earth metal is calcium, said reaction product has an alkalinity value in the range of 130 to 450, from 4 to 12 weight percent calcium, and from 0.1 to 5 weight percent nitrogen.
 2. A sulfurized alkyl phenol of the formula:
 2. A sulfurized alkylphenol of the formula:
 2. A SULFURIZED ALKYL PHENOL OF THE FORMULA:
 3. AN ALKALINE EARTH METAL BASE WHEREIN THE ALKALINE EARTH METAL IS SELECTED FROM THE GROUP CONSISTING OF CALCIUM AND BARIUM, WHEREIN THE REACTION OF SAID MANNICH BASE WITH SAID SULFURIZED ALKYLPHENOL AND SAID ALKALINE EARTH METAL BASE IS CONDUCTED AT A TEMPERATURE BETWEEN ABOUT 125*C TO ABOUT 200*C AND IN THE PRESENCE OF ETHELENE GLYCOL WHICH IS REMOVED FROM THE REACTION, SYSTEM UPON COMPLETION OF THE REACTION, AND WHEREIN THE RATIO OVER THE ENTIRE REACTION PRODUCT OF THE EQUIVALENTS OF ALKYLPHENOL FROM THE SAID MANNICH BASE TO EQUIVALENTS OF ALKYLPHENOL FROM THE SAID SULFURIZED ALKYLPHENOL IS FROM 0.2-5:1, THE SAID ALKALINE EARTH METAL BASE IS USED IN A AMOUNT TO PROVIDE A TOTAL OF FROM 1 TO ABOUT 1.75 EQUIVALENTS OF SAID ALKALINE EARTH METAL BASE PER WQUIVALENT OF ALKYLPHENOL, AND A SLUTION OF SAID REACTION PRODUCT AT A CONCETRATION OF 0.88 FORMAL OF CALCIUM OR BARIUM IN A 100 NEUTRAL OIL HAS A VISCOSITY OF 210*F IN THE RANGE OF ABOUT 200 TO 3,000 SUS.
 3. The reaction product according to claim 1, wherein R4 is methyl.
 3. A calcium base; wherein the reaction of said Mannich base with said sulfurized alkylphenol and said calcium base is conducted at a temperature of 125* to 160*C and in the presence of ethylene glycol which is removed from the reaction system upon the completion of the reaction, and wherein the ratio over the entire reaction product of the equivalents of alkylphenol from the said Mannich base to equivalents of alkylphenol from the said sulfurized alkylphenol is from 0.3-3;1, the said calcium base is used in an amount to provide a total of from 1 to about 1.75 equivalents of said calcium base per equivalent of alkylphenol, and the solution of said reaction product at a concentration of 0.88 formal of calcium or barium in a 100 neutral oil has a viscosity at 210*F in the range of about 500 to 1,500 SUS.
 3. An alkaline earth metal base wherein the alkaline earth metal is selected from the group consisting of calcium and barium; wherein the reaction of said Mannich base with said sulfurized alkylphenol and said alkaline earth metal base is conducted at a temperature between about 125*C to about 200*C and in the presence of ethylene glycol which is removed from the reaction system upon completion of the reaction, and wherein the ratio over the entire reaction product of the equivalents of alkylphenol from the said Mannich base to equivalents of alkylphenol from the said sulfurized alkylphenol is from 0.2-5:1, the said alkaline earth metal base is used in an amount to provide a total of from 1 to about 1.75 equivalents of said alkaline earth metal base per equivalent of alkylphenol, and a solution of said reaction product at a concentration of 0.88 formal of calcium or barium in a 100 neutral oil has a viscosity of 210*F in the range of about 200 to 3,000 SUS.
 4. The reaction product according to claim 1, wherein R4 is methyl, said ratio is 0.3-3:1, and said alkaline earth metal is calcium.
 5. The reaction product according to claim 1, wherein said alkaline earth metal base is calcium hydroxide, R4 is methyl, and said reaction product has an alkalinity value of 175 to 400 mg. KOH/g., has from 0.5 to 4 weight percent nitrogen, 2 to 8 weight percent sulfur, and the solution of said reaction product in a 100 neutral oil at a calcium concentration of 0.88 formal has a viscosity in the range of 500 to 1,500 SUS at 210*F.
 6. The reaction product according to claim 1, wherein said alkaline earth metal is calcium, R4 is methyl, said reaction product has from 0.5 to 4 weight percent nitrogen, from 2 to 8 weight percent sulfur, from 5 to 10 weight percent calcium, and an alkalinity value of from 175 to 400, and wherein said ratio is 0.3-2:1.
 7. The reaction product according to claim 6, wherein R2 and R3 are polypropyl of from about 12 to 15 carbon atoms, and said alkaline earth metal base is Ca(OH)2.
 8. A reaction product of 